Fungicidal composition and method containing alpha-halosulfonium ylids and alpha-halosulfonium salts



United States Patent Int. Cl. A01n 9/12 U.S. Cl. 424--331 4 Claims ABSTRACT OF THE DISCLOSURE A fungicidal composition and method containing ochalosulfoninm compounds which are represented by a formula selected from the group consisting of (a) norm X o M Q 11 cm a R and RCHz X o 3Hdma, R2, Ra

wherein R and R are each selected from the group consisting of hydrogen, alkyl of not more than 12 carbon atoms and haloalkyl of not more than 12 carbon atoms containing 1, 2 or 3 halogen atoms, X is halogen (Cl, Br and I), R is selected from. the group consisting of halogen (Cl, Br, F and I) and alkyl of not more than 4 carbon atoms, R is selected from the group consisting of N0 and alkoxy of not more than 4 carbon atoms, R is phenyl, a is an integer from 0 to 5 inclusive, b is an integer from 0 to 2 inclusive and c is an integer from O to 1.

represented by a formula selected from the group consisting of and 3,538,229 Patented Nov. 3, 1970 ice wherein R and R are each selected from the group consisting of hydrogen, alkyl of not more than 12 carbon atoms and haloalkyl of not more than 12 carbon atoms containing 1, 2 or 3 halogen atoms, X is halogen (Cl, Br and I), R is selected from the group consisting of halogen (Cl, Br, F and I) and alkyl of not more thtan 4 carbon atoms, R is selected from the group consisting of N0 and alkoxy of not more than 4 carbon atom, R is phenyl, a is an integer from 0 to 5 inclusive, b is an integer from O to 2 inclusive and c is an integer from 0 to 1.

In the above formula, R and R can be hydrogen, alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.- butyl, isobutyl, tert-butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and the various homologues and isomers of alkyl having from 1 to 12 carbon atoms, and haloalkyl such as chloromethyl, iodomethyl, bromomethyl, fluoromethyl, chloroethyl, iodoethyl, bromoethyl, fluoroethyl, trichloromethyl, diiodoethy'l, tribromomethyl, trifluoromethyl, dichloroethyl, chloro-n-propyl, brorno-n-propyl, iodoisopropyl, bromo-n-butyl, bromo-tert-butyl, 1,3,3- trichlorobutyl, 1,3,3-tribromobuty1, chloropentyl, bromopentyl, 2,3 dichloropentyl, 3,3 dibromopentyl, chlorohexyl, bromohexyl, 2,4-dichlorohexyl, 1,3-dibromohexyl, 1,3,4-trichlorohexyl, chloroheptyl, bromoheptyl, fluoroheptyl, 1,3-dichloroheptyl, 1,4,4-trichloroheptyl, 2,4-di- (chloromethyl)heptyl, chlorooctyl, bromooctyl, iodooctyl, 2,4-di(chloromethyDhexyl, 2,4 dichlorooctyl, 2,4,4-tri- (chloromethyl)pentyl 1,3,5-tribromooctyl and the halogenated straight and branched chain nonyl, decyl, undecyl and dodecyl. In the above formulae R and R are pref: erably hydrogen, lower alkyl (1 to 4 carbon atoms) or lower haloalkyl (l to 4 carbon atoms).

In the above formulae R as alkyl can be the alkyl disclosed above for R and R of not more than 4 carbon atoms. As alkoXy, R can be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and tertbutoxy.

The u-halosulfonium salts of this invention are prepared by a process which comprises halogenation of a sulfonium ylid in accordance with the following representative synthesis R4, Rent s=ono +X2 a ong R2, R31,

R RCH: 2 v oHc worn Ra Ra.

wherein R, R R R R X, a, 12 and c are as define above.

Halogenation in accordance with this invention is carried out by admixing substantially equimolar amounts of reactants in the presence of an inert organic medium at room temperature, i.e. about 20 C. to 25 C. However, higher or lower temperatures can be employed, the temperature not being critical.

Suitable inert organic media which can be used in the prepartion of the ot-halosulfonium salts of this invention include by way of example hydrocarbons such as benzene, toluene, Xylene, cyclohexane, methylcyclohexane, n-heptane, n-hexane and the like; ethers such as isopropyl ether, n-butyl ether, 1,4-dioxane, isobutyl ether, diethyl ether and the like; aliphatic and cycoaliphatic ketones such as methyl isopropyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, diisopropyl ketone, cyclohexanone and the like; and organic halides such as carbon tetra-chloride, n-butyl chloride, ethylene dichloride, and the like.

The a-halosulfonium ylids of the present invention are prepared by a process which comprises reacting an OL-halO- sulfonium salt of the formula wherein R, R R R R X, a, b and c are as defined above with a substantially equimolar amount of an alkali metal hydride such as sodium hydride under substantially anhydrous conditions in the presence of an inert organic media until a substantially equimolar amount of hydrogen has evolved. The process is suitably carried out at room temperature, i.e. about 20 C. to 25 C. However, higher or lower temperatures can be used, the temperature not being critical. Inert organic media for use in this invention include, for example, tetrahydrofuran, diglyme, diethylether and the like.

Pressure is not a critical factor in either of the above processes of this invention. Pressure both above and below atmospheric can be employed although atmospheric pressure is preferred for convenience.

The separation of the resulting a-halosulfonium ylids or a-halosulfonium salts from the reaction mixture is readily accomplished. The a-halosulfonium salts are separated from the reaction mixture by filtration or decantation. In some cases it may be necessary to remove the solvent from the resulting filtrate by stripping or distillation, preferably low temperature vacuum distillation, to recover all of the product salts. The a-halosulfonium ylids are separated from the reaction mixture by removing the alkali metal halide salt formed during the reaction by filtration and the solvent from the filtrate by Stripping or distillation. The product ylids and salts can be purified by any of the conventional means well known in the art, e.g. selective extraction, recrystallization or a combination of these methods.

The u-halosulfonium ylids and whalosulfonium salts of this invention are crystalline solid materials which are insoluble in water but somewhat soluble in many organic solvents, for example, alcohols, ketones, hydrocarbons such as benzene, toluene, xylene and the like and chlorohydrocarbons such as chlorobenzene, carbon tetrachloride and the like.

The following examples illustrate the invention. Parts and percent are by weight unless otherwise indicated.

EXAMPLE 1 To a suitable reaction vessel charged with about 4.5 parts of dimethylsulfonium phenacylide and 50 parts of trichloromethane is added 4.0 parts of bromine with stirring at room temperature (about 20 C.). At the end of the bromine addition, the reaction mixture is filtered and the solids (4.35 parts) are crystallized from methyl alcohol to give (a-bromophenacyl) dimethylsulfonium bromide, M.P. 124125 C.

Calcd. for C H Br SO (percent): C, 35.31; H, 3.56; Br, 47.00; S, 9.43. Found (percent): C, 35.23; H, 3.38; Br, 47.05; S, 9.61.

Following substantially the same procedure as in the foregoing example the following a-halosulfonium salts of this invention are prepared.

Example (ix-chlorophenacyl) dimethylsulfonium chloride (oi-iodophenacyl) dimethylsulfonium iodide (on chloro 4 chlorophenacyl) dimethylsulfonium chloride (or chloro-2,4-dichlorophenacyl) dimethylsulsulfonium chloride (at chloro -2,4,6-trichlorophenacyl) dimethylsulfonium chloride (at chloro 4 methylphenacyl) dimethylsulfonium chloride 11 (a chloro 2,5-diethylphenacyl) dimethylsulfonium chloride 12 (a-chloro-2,6-di-tert-butylphenacyl) dimethylsulfonium chloride 13 (a chloro 4 bromophenacyl) dimethylsulfonium chloride 14 (or chloro-3,S-dibromophenacyl) dimethylsulfonium chloride 15 (a chloro-2-iodophenacyl) dimethylsulfonium chloride 16 (a chloro 2,6-difluorophenacyl) dimethylsulfonium chloride 17 (a chloro-2,5-dimethylphenacyl) dimethylsulfonium chloride 18 (a chloro-3,S-dimethylphenacyl) dimethylsulfonium chloride 19 (0c chloro 2,3,4,5,6-pentachlorophenacyl) dimethylsulfonium chloride 20 (a chloro-4-nitrophenacyl) dimethylsulfonium chloride 21 (a chloro 2,4-dimitrophenacyl) dimethylsulsulfonium chloride 22 (a chloro 4-methoxyphenacyl) dimethylsulfonium chloride 23 (a-chloro-2,4-dimethoxyphenacyl) dimethylsulfonium chloride 24 (a-chloro-2,S-dimethoxyphenacyl) dimethylsulfonium chloride 25 (a chloro 4 n-butoxyphenacyl) dimethylsulfonium chloride 26 (a-chloro-4-phenylphenacyl) dimethylsulfonium chloride 27 (a chloro-2-methyl-4-nitrophenacyl) dimethylsulfonium chloride 28 (a chloro 2 methoxy-4-chlorophenacyl) dimethylsulfonium chloride 29 (a fluoro 2 methyl-4-methoxyphenacyl) dimethylsulfonium chloride 30 (a-bromophenacyl) diethylsulfonium bromide 31 (a-bromophenacyl) di(n-butyl)sulfonium bromide 32 (a-bromophenacyl) di(n-octyl)sulfonium bromide 3 3 (a-bromophenacyl) di (2-chloroethyl sulfonium bromide 34 (a iodophenacyl) di(3-chlorobutyl)sulfonium bromide 35 (a chlorophenacyl) di(n dodecyl)sulfonium chloride 36 (a chloro 4-chlorophenacyl) di(4,4-dichloropentyl) sulfonium chloride 3 7 (or-chlorophenacyl) di 2,2,4-tribromobutyl) sulfonium chloride 38 (a chlorophenacyl) di(2 fiuor0pentyl)sulfonium chloride 39 (a chlorophenacyl) di(2-iodoethyl)sulfonium chloride 40 (a bromo 2,4-dimethylphenacyl) diethylsulfonium bromide EXAMPLE 41 A suitable reaction vessel is charged with about 750 parts of tetrahydrofuran, 17.0 parts of (a-bromophenyl) dimethylsulfonium bromide and 2.3 parts of sodium hydride. The reaction mixture is stirred at room temperature until the evolution of hydrogen is substantially complete. The reaction mixture is filtered to remove the solids which are then extracted with methylene chloride. The

Example 42 dimethylsulfonium a-chlorophenacylide 43 dimethylsulfonium wiodophenacylide 44 dimethylsulfonium a-bromo-4-chlorophenacylide 45 dimethylsulfonium a-bromo-2,4-dichlorophenacylide 46 dimethylsulfonium a-bromo-2,4,6'-trichlorophenacylide 47 dimethylsulfonium a-chloro-4-methylphenacylide 48 dimethylsulfonium ot-chloro-4-tert-butylphenacylide 49 dimethylsulfonium a-ch1oro-2,4-dimethy1phenacylide 50 dimethylsulfonium u-chloro-2,4,6-trimethylphenacylide 51 dimethylsulfonium u-chloro-2,5-diethylphenacylide 52 dimethylsulfonium a-chloro-2,6-di(tert-butyl) phenacylide 53 dimethylsulfonium u-bromo-4-bromophenacylide 54 dimethylsulfonium a-bromo-3,5-dibromophenacylide 55 dimethylsulfonium u-bromo-2-iodophenacylide 56 dimethylsulfoniurn a-bromo-2,6-difluorophenacylide 57 dimethylsulfonium achloro-2,S-dimethylphenacylide 58 dimethylsulfonium ot-chloro-3,5-dimethylphenacylide Y 59 dimethylsulfonium a-chloro-2,3,4,5,6-pentachlorophenacylide 60 dimethylsulfonium ot-bromo-4-nitrophenacylide 61 dimethylsulfonium u-brorno-2,4-dinitrophenacylide 62 dimethylsulfonium a-bromo-4-methoxyphenacylide 63 dimethylsulfonium d-bromo-ZA-dimethoxyphenacylide 64 dirnethylsulfonium a-bromo-2,5-dimethoxyg phenacylide 65 dimethylsulfonium a-chloro-4-n-butoxyphenacylide 66 dimethylsulfonium u-chloro-4-phenylphenacylide 67 dimethylsulfonium a-chloro-2-methyl-4-nitrophenacylide 68 dimethylsulfom'um wchloro-2-methoxy-4-ch1oro phenacylide 69 dimethylsulfonium a-chloro-2-methyl-4-methoxyphenacylide 70 diethylsulfoniurn a-bromophenacylide 71 di(n-butyl)sulfonium u-bromophenacylide Y 72 di(n-octyl)sulfonium a-bromophenacylide 73v di(2-chloroethyl)sulfonium u-bromophenacylide 74 di 3-chlorobutyl) sulfonium a-bromophenacylide 75 di(n-dodecyl)sulfonium a-bromophenacylide 76 di(4,4-dichloropentyl)sulfonium u-chloro-4- chlorophenacylide 77 di(2,2,4-tribromobutyl)sulfonium a-chlorophenacylide 78 di(2-fluoropentyl)sulfonium a-chlorophenacylide 79 di(2-iodoethyl) sulfonium a-chlorophenacylide 80 diethylsulfonium otbromo-2,4-dimethylphenacylide The sulfonium ylids used as starting materials in the preparation of the a-halosulfonium salts of this invention and processes for making them are disclosed and claimed in application Ser. No. 549,166, now US. Pat. No. 3,359,322, filed of even date herewith. Said process comprises reacting a sulfonium salt of the formula worn R 3,,

wherein R, R R R R, X, a, .b and c are as defined above with a substantially equimolar amount of an alkaline material such as sodium hydride or sodium hydroxide in the presence of an inert liquid medium such as an aqueous medium or organic medium. Temperature is not critical and room temperature is usually employed.

The a-halosulfonium ylids and OL'hfilOSlllfOIliUHl salts of this invention are useful for various purposes such as fire retardants, rust inhibitors, rust removers, tanning agents and water-insoluble dispersion agents, and as chemical intermediate for petroleum additives and agricultural chemicals. For example, the a-halosulfonium ylids and a-halosulfonium salts of this invention are useful as pesticides, particularly fungicides. In practicing the fungicidal methods of this invention, one or more of the present whalosulfonium ylids or a-halosulfonium salts is applied to the fungal organisms or the material to be treated for the control of fungi in an amount sufficient to exert fungicidal activity. The fungicidal sulfonium compounds of this invention are particularly effective when applied directly to the soil for control of soil borne fungal organisms. They are also effective in the treatment of plant life such as vegetables, ornamental plants and fruit-bearing trees; organic fibers and fabrics; leather; paints and lubricating oils and various cellulosic materials such as wood. In application to soil and plants, fungicidal control is obtained in most instances by the application of from about 0.01 pound to about 25 pounds of active ingredient per acre. The preferred amount is determined by and dependent upon the particular fungicidal compound selected, the method of application, and in the case of application to plant life, the state and condition of growth and the climatic conditions.

The fungicidal activity of the whalosulfonium compounds of the invention is demonstrated as follows.

An intimate mixture of 2 volumes of yellow corn meals and 3 volumes of white sand is infested with a particular pathogen (below itemized) and incubated for two weeks at 20 C. Then one volume of this infested mixture is blended uniformly with 3 volumes of a good grade of top soil which had been sterilized. To accomplish complete blending the composite of soil and infested mixture is passed through a N0. 8 screen three times. A number of small cups are then tightly packed with 30 gram portions of the composite and the surface thereof leveled.

A sufficient amount of (a-iodophenacyl)dimethylsulfonium iodide is dissolved in acetone to make a 1% by weight solution which is then diluted with waterto provide a formulation having a concentration of 0.1% by Weight. To provide the desired concentration in the aforedescribed soil composite the following further dilutions with water are made:

Conc. desired in soil in ppm 30 Ml. of 0.1% formulation 1 M1. of water added to formulation 3 The 4 ml. portions are drenched over the surface of the soil in each cup, care being taken to insure even distribution. The cups are then placed in a humidity chamber at 70 F. for 44 hours. Upon removal from the chamber the amount of mycelial growth on the surface of the soil is noted and rated as follows:

1no growth 2-growth from corn meal only 3-some growth in soil away from corn meal particles 4surface covered but little aerial growth 5growth equivalent to that on untreated soil.

The results obtained with (a-iodophenacyl)dimethyl sulfonium iodide at a soil concentration of 30 p.p.m. are set forth below for each of the two indicated fungal organisms:

Fungal organism: Rating Pythium ultimum 1 Rhizoctonia solani 1 The fungicidal compositions of this invention contain at least one active ingredient and a material referred to in the art as a fungicidal adjuvant in liquid or solid form. The fungicidal compositions are prepared by ad mixing the active ingredient with an adjuvant including diluents, extenders, carriers and conditioning agents to provide compositions in the form of finely-divided particulate solids, granules, pellets, solutions, aerosols and aqueous dispersions or emulsions. Thus the active ingredient can be used with an adjuvant such as a finely-divided particulate solid, at liquid of organic origin, water, a wetting agent, dispersing agent, an emulsifying agent or any suitable combination of these.

Typical finely-divided solid carriers and extenders which can be used in the fungicidal compositions of this invention include, for example, the tales, clays, pumice, silica, diatomaceous earth, charcoal, quartz. Fullers earth, salt, sulfur, powdered cork, powdered wood, walnut flour, chalk, tobacco dust, volcanic ash, and the like. Typical liquid diluents include, for example Water, kerosene, Stoddard solvent, hexane, benzene, toluene, acetone, ethylene dichloride, xylene, alcohols, diesel oil, glycols and the like. Typical diluents for aerosols include, for example, Freons such as dichlorolluoromethane, trichlorofluoromethane, and the like.

The fungicidal compositions of this invention, particularly liquids and wettable particles, usually contain as a conditioning agent one or more surface-active agents in amounts sufficient to render a given composition readily dispersible in water or in oil. By the term surface-active agent it is understood that wetting agents, dispersing agents, suspending agents, emulsifying agents and the like are included therein.

The surface-active agents employed can be of the anionic, cationic or nonionic type. They include, for example, sodium oleate, sulfonated petroleum oils, alkyl aryl sulfonates, sodium lauryl sulfate, polyethylene oxides, lignin sulfonates, and other surface-active agents.

The fungicidal compositions of this invention generally contain from about 0.005% to about 95% by weight of the active fungicidal ingredient.

The fungicidal compounds of the present invention can be employed in combination with other fungicides to give compositions that have broad spectrum fungicidal activity. In these mixtures, the auxiliary fungicidally active materials can be present in any desired amount, ordinarily from about 0.1 to about 20 parts by weight per 1 part by weight of a compound of the present invention. In some instances it may even be desirable to employ two or more auxiliary fungicides.

Typical of the auxiliary fungicides that can be employed in combination with the compounds of the present invention are the following:

N-trichloro-methylthio-4-cyclohexene-1,2-dicarboximide Tetramethylthiuram disulfide Manganese ethylene-bis-dithiocarbam ate Ferric dimethyl dithiocarbamate Zinc ethylene-bis-dithiocarbamate Zinc dimethyl dithiocarbamate Tetra copper calcium oxychloride Tetrachloro-p-benzoquinone 2,3-dich1oro-1,4-naphthoquinone 2-dichlono-6-(o-chloroanilino)triazine Ethylene thiuram monosulfide Z-Heptadecyl glyoxalidine acetate Ferric dimethyl dithiocarbamate pl us 2-mercaptobenzothiazole Manganese dimethyl dithiocarbamate plus 2-mercaptobenzothiazole Copper dihydrazinium sulfate Oopper-S-quinolinolate Cycloheximide Terramycin Streptomycin When operating in accordance with the present invention, the whalosulfonium compounds or a composition containing them can be applied to the fungal organisms to be controlled, or to their habitats in any convenient fashion, e.g. by means of hand dusters or Sprayers. Applications to the above-ground portions of plants conveniently can be carried out with powder dusters, boom sprayers and spray dusters. In foliar applications, the employed compositions should not contain any appreciable amount of phytotoxic diluents. In large scale operations, dusts or low volume sprays may be applied from airplanes.

The term fungicidal composition as used herein and in the appended claims is intended to mean not only compositions in a suitable form for application but also concentrated compositions which require dilution or extension with a suitable quantity of liquid or solid adjuvant prior to application.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A fungicidal composition comprising a fungicidally effective amount of a compound having a formula selected from the group consisting of H. CH2 R b and R CH

wherein R and R are each selected from the group consisting of hydrogen, alkyl or not more than 12 carbon atoms and haloalkyl of not more than 12 carbon atoms containing from 1 to 3 halogen atoms, X is selected from the group consisting of Cl, Br and I, R is selected from the group consisting of halogen and alkyl of not more than 4 carbon atoms, R is selected from the group consisting of N0 and alkoxy of not more than 4 carbon atoms, R is phenyl, a is an integer from 0 to 5 inclusive, b is an integer from 0 to 2 inclusive and C is an integer from 0 to 1 and an inert carrier.

2. Composition of claim 1 wherein the compound is (a-iodophenacyl) dimethylsulfonium iodide.

3'. A fungicidal method of controlling fungal organisms which comprises applying to said organisms a fungicidally effective amount of a compound having a formula selected from the group consisting of 9 10 and 4. Method of claim 3 wherein the compound is (a-iodo- R40 phenacyl) dimethylsulfonium iodide. Rom X o X- References Cited g, m 5 UNITED STATES PATENTS wherein R and R are each selected from the group con- 3,359,322 12/1967 Ram 260 592 sisting of hydrogen, alkyl of not'more than 12 carbon OTHER REFERENCES atoms and haloalkyl of not more than 12 carbon atoms containing from 1 to 3 halogen atoms, X is selected from 10 2 Amencan Chemlcal Soclety the group consisting of Cl, Br and I, R is selected from V the group consisting of halogen and alkyl of not more than 4 carbon atoms, R is selected from the group con- ALBERT MEYERS Pnmary Exammer sisting of N0 and alkoxy of not more than 4 carbon ORE, Assistant EXamiIler atoms, R; is phenyl, a is an integer from 0 to 5 inclusive, 15

b is an integer from O to 2 inclusive and c is an integer US from 01:0 1. 424 46 357 

